Co-Mo/γ-Al<sub>2</sub>O<sub>3</sub>催化剂的原位红外光谱表征研究

张玉涵; 凌凤香; 王少军; 赵国利

Co-Mo/γ-Al₂O₃催化剂的原位红外光谱表征研究

1.
辽宁石油化工大学化学与材料科学学院, 辽宁抚顺 113001;
2.
抚顺石油化工研究院, 辽宁抚顺 113001

详细信息

通讯作者:
凌凤香, Tel: 024-56389578, E-mail: lingfengxiang.fshy@sinopec.com。

中图分类号: O657.33
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- 被引次数: 0
出版历程
- 收稿日期: 2012-11-06
- 修回日期: 2013-01-08
- 刊出日期: 2013-06-30

An in-situ FT-IR study on the CO and NO co-adsorption on the Co-Mo/γ-Al₂O₃ catalysts

1.
Liaoning Shihua University, Fushun 113001, China;
2.
Fushun Research Institute of Petroleum and Petrochemicals, SINOPEC, Fushun 113001, China

摘要

摘要: 采用CO和NO作为探针分子,应用原位红外光谱法(in-situ FT-IR)和程序升温还原(H₂-TPR)对Mo/γ-Al₂O₃和Co-Mo/γ-Al₂O₃加氢催化剂进行表征,并对催化剂进行了加氢脱硫(HDS)活性评价。实验结果表明,在Co-Mo/γ-Al₂O₃催化剂表面存在三个吸附位;在Mo/γ-Al₂O₃催化剂中加入助剂钴对钼吸附位起到显著的改性作用,并且引入新的活性中心,提高了催化剂的催化活性;随着钼含量的增加,活性中心数目逐渐增多;用CO-NO共吸附原位红外光谱研究了Co-Mo/γ-Al₂O₃催化剂表面活性中心的信息,证明不同的Mo中心分别吸附CO和NO,并将它们区分开来,解决了不同活性中心的光谱互相重叠的问题。
- Co-Mo/&gamma /
- -Al₂O₃催化剂 /
- 原位红外光谱 /
- 探针分子 /
- 活性中心
Abstract: The active sites of reduced Mo/γ-Al₂O₃ and Co-Mo/γ-Al₂O₃ hydrotreating catalysts were studied by in-situ FT-IR using CO and NO as probe molecules; the results were correlated with their activity in hydrodesulfurization (HDS) and behavior in temperature programmed reduction (H₂-TPR). The results indicate that there exist three main adsorption sites on the surface of Co-Mo/γ-Al₂O₃ catalysts. The addition of cobalt to Mo/γ-Al₂O₃ is able to modify Mo sites and to introduce active Co sites; an increase of the molybdenum content may also increase the number of active sites and improve the catalytic activity of Co-Mo/γ-Al₂O₃. FT-IR spectra of CO and NO co-adsorption is able to distinguish the spectra overlapping of different active sites, which reveals that CO and NO are actually adsorbed on different Mo active sites.
- Co-Mo/&gamma /
- -Al₂O₃ catalysts /
- in-situ FT-IR /
- probe molecules /
- active sites

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参考文献(25)

姚国欣, 刘伯华. 21世纪的炼油技术和炼油厂(2)[J]. 炼油设计, 2001, 31(2): 1-7. (YAO Guo-xin, LIU Bo-hua. Petroleum refining techniques and refineries in 21^st century(2)[J]. Petroleum Refinery Engineering, 2001, 31(2): 1-7.)

郑宇印, 刘百军. 加氢精制催化剂研究新进展[J]. 工业催化, 2003, 11(7): 1-6. (ZHENG Yu-yin, LIU Bai-jun. Recent advances in development of hydrotreating catalysts[J]. Industrial Catalysis, 2003, 11(7): 1-6.)

郭金涛, 田然, 张志华, 张文成. 新型体相柴油加氢精制催化剂的研制[J]. 石油炼制与化工, 2010, 41(6): 26-29. (GUO Jin-tao, TIAN Ran, ZHANG Zhi-hua, ZHANG Wen-cheng. Research of a new bulk catalyst for gas oil hydrotreating[J]. Petroleum Processing and Petrochemicals, 2010, 41(6): 26-29.)

辛勤. 催化研究中的原位技术[M]. 北京: 北京大学出版社, 1993: 149-164. (XIN Qin. In-situ technology in catalysis studies[M]. Beijing: Peking University Press, 1993: 149-164.)

RYCZKOWSKI J. IR spectroscopy in catalysis[J]. Catal Today, 2001, 68(4): 263-381.

辛勤, 梁长海. 固体催化剂的研究方法[J]. 石油化工, 2001, 30(1): 72-85. (XIN Qin, LIANG Chang-hai. Research methods for solid catalysts[J]. Petrochemical Technology, 2001, 30(1): 72-85.)

尹元根. 多相催化剂的研究方法[M]. 北京: 化学工业出版社, 1988: 545-604. (YIN Yuan-gen. Research methods for heterogeneous catalysts[M]. Beijing: Chemical Industry Press, 1988: 545-604.)

左东华, MAUGÉ F, 聂红, VRINAT M, 石亚华, LACROIX M, 李大东. 硫化态NiW/Al₂O₃催化剂加氢脱硫活性相的研究III. 低温CO吸附-原位红外光谱表征[J]. 催化学报, 2004, 25(5): 377-383. (ZUO Dong-hua, MAUGÉ F, NIE Hong, VRINAT M, SHI Ya-hua, LACROIX M, LI Da-dong. Study on the hydrodesulfurization active phase in sulfided NiW/Al₂O₃catalyst III. Low-temperature FT-IR spectroscopy of adsorbed CO[J]. Chinese Journal of Catalysis, 2004, 25(5): 377-383.)

TRAVERT A, DUJARDIN C, MAUGÉ F, VEILLY E, CRISTOL S, PAUL J F, PAYEN E. CO adsorption on CoMo and NiMo sulfide catalysts: A combined IR and DFT study[J]. J Phys Chem B, 2006, 110(3): 1261-1270.

张新堂, 李欣, 孙海燕, 谭永放, 纵秋云, 毛鹏生. Co-Mo/Al₂O₃耐硫变换催化剂的表征研究[J]. 燃料化学学报, 2003, 31(1): 65-69. (ZHANG Xin-tang, LI Xin, SUN Hai-yan, TAN Yong-fang, ZONG Qiu-yun, MAO Peng-sheng. Studies on the characterization of Co-Mo/Al₂O₃ sulfur-tolerant CO shift catalyst[J]. Journal of Fuel Chemistry and Technology, 2003, 31(1): 65-69.)

EISCHENS R P, PLISKIN W A. The infrared spectra of adsorbed molecules[J]. Adv Catal, 1958, 10: 1-56.

辛勤, 罗孟飞. 现代催化研究方法[M]. 北京: 科学出版社, 2009: 289-290. (XIN Qin, LUO Meng-fei. Modern research methods for catalysis [M]. Beijing: Science Press, 2009: 289-290.)

张新堂, 李欣, 谭永放, 纵秋云, 毛鹏生. 耐硫变换催化剂中活性组分钴、钼的相互作用[J]. 燃料化学学报, 2001, 29(6): 528-531. (ZHANG Xin-tang, LI Xin, TAN Yong-fang, ZONG Qiu-yun, MAO Peng-sheng. Interaction between Co and Mo active components of sulfur-tolerant CO conversion catalyst[J]. Journal of Fuel Chemistry and Technology, 2001, 29(6): 528-531.)

HADJIIVANOV K I, VAYSSILOV G N. Characterization of oxide surfaces and zeolites by carbon monoxide as an IR probe molecule[J]. Adv Catal, 2002, 47: 307-511.

GAO X T, XIN Q. Spectroscopic determination of oxidation and coordination states of Mo cations in the reduced Mo/Al₂O₃ catalyst[J]. J Catal, 1994, 146(2): 306-309.

李新生, 辛勤, 郭燮贤. 利用CO和NO探针分子的红外光谱研究钴和钌的助剂作用[J]. 燃料化学学报, 1990, 19(4): 327-332. (LI Xin-sheng, XIN Qin, GUO Xie-xian. Study on the promotion effects of cobalt and ruthenium by IR-spectoscopy of CO and NO coadsorption[J]. Journal of Fuel Chemistry and Technology, 1990, 19(4): 327-332.)

VAKROS J, LYCOURGHIOTIS A, VOYIATZIS G A, SIOKOU A, KORDULIS C. CoMo/Al₂O₃-SiO₂ catalysts prepared by co-equilibrium deposition filtration: Characterization and catalytic behavior for the hydrodesulphurization of thiophene[J]. Appl Catal B: Environ, 2010, 96(3-4): 496-507.

RAJAGOPAL S, MARINI H J, MARZARI J A, MIRANDA R. Silica-alumina-supported acidic molybdenum catalysts-TPR and XRD characterization[J]. J Catal, 1994, 147(2): 417-428.

ARNOLDY P, FRANKEN M C, SCHEFFER B. Temperature-programmed reduction of CoO-MoO₃/Al₂O₃ catalysts[J]. J Catal, 1985, 96(2): 381-395.

ARNOLDY P, MOULIJN J A. Temperature-programmed reduction of CoO/Al₂O₃catalysts[J]. J Catal, 1985, 93(1): 38-54.

LÓPEZ-CORDERO R, GIL-LAMBIAS F J, LÓPEZ-AGUDO A. Temperature-programmed reduction and zeta potential studies of the structure of MoO₃/Al₂O₃ and MoO₃/SiO₂ catalysts effect of the impregnation pH and molybdenum loading[J]. Appl Catal, 1991, 74(1): 125-136.

谭永放, 郝树仁, 张新堂, 郭建学. Co-Mo系耐硫变换催化剂的TPR表征[J]. 工业催化, 1999, 7(2): 58-63. (TAN Yong-fang, HAO Shu-ren, ZHANG Xin-tang, GUO Jian-xue. TPR characterization of Co-Mo sulfur-tolerant shift catalysts[J]. Industrial Catalysis, 1999, 7(2): 58-63.)

PORTELA L, GRANGE P, DELMON B. The adsorption of nitric oxide on supported Co-Mo hydrodesulfurization catalysts: A review[J]. Catal Rev, 1995, 37(4): 699-731.

肖丰收, 应品良, 辛勤, 郭燮贤. 利用CO和NO吸附的红外光谱表征还原态的Ru-Co-Mo/Al₂O₃催化剂[J]. 燃料化学学报, 1992, 20(2): 113-117. (XIAO Feng-shou, YING Pin-liang, XIN Qin, GUO Xie-xian. An infrared characterization of reduced Ru-Co-Mo/Al₂O₃ catalyst by CO and NO adsorption[J]. Journal of Fuel Chemistry and Technology, 1992, 20(2): 113-117.)

辛勤, 魏昭彬, 张卫民, 盛世善. 利用TPD-MS、IR和XPS表征还原态Co-Mo/Al₂O₃[J]. 物理化学学报, 1990, 6(4): 418-424. (XIN Qin, WEI Zhao-bin, ZHANG Wei-min, SHENG Shi-shan. Characterization of reduced state of Co-Mo/Al₂O₃ by TPD-MS, IR and XPS[J]. Acta Physico-Chimica Sinica, 1990, 6(4): 418-424.)

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